Composite fabrics bonded together with polyvinyl chloride



Oct. 21, 1952 EWlNG ET AL 2,614,954

COMPOSITE FABRICS BONDED TOGETHER WITH POLYVINYL CHLORIDE Filed Sept. 21, 1948 lave/7:013

Patented Oct. 21; 1952 OFFICE 'CGMPQSQEF iimcs BONDED TOGETHER rwm'ur uzvm ncnnonmn H-e'nfi wmgeiia Klimtv Menbr, Spoiidon, ear

ease "with we eyclo hex'anol arid'inethyl cyclo hexane: phcha at-esmentioned above.

Tl ie estere seeeific'a'lly mentioned above ,are neural esters er di'efboxylie acids with monosebacie aci d). l rferably qhe slim f th'e caibii atoms "in the giyeoi- =ino1ecu1e te ge fiher "t'hd e in the acid mblecule should ;notexceed 12 'Q1 16. The I resinous 1 plasti ciser; seld under the -trade v. name Paraplex-Glfa-appears to beva yproduct-oi this kind derived" fronrsebacic' acid a'nd glycol and isvery suitable 'formhe =purpes'es ofihe-inventibn.

The? polyesters "may be made by heatmg one meleculaf; bropertion' of -the acid with; s'ubstantiaJll'y mer thanvofie 'molecular proportion: 'ofthe glycol and dis 'i-x dfi waterend' g'ly'cbl fifitil a product (if the' desired"melecularvw'eight iswd'btamed;

to impart to the material an odour which is un desirable in some cases.

Plasticisers of the kind referred to above as imparting adhesion, if used as the sole plasticiser in a polyvinyl chloride composition give films and coatings which are somewhat limp and insufciently resilient for some purposes. To give more resilient films or coatings these plasticisers may be used in conjunction with plasticisers having relatively long inactive chains attached to active groups as in the esters of polycarboxylic acids (including'dicarboxylic acids) with saturated alcohols of at least 6 carbon atoms or in the esters of polyhydric alcohols (including di-hydric alcohols) with saturated monocarboxylic acids of at least 6 carbon atoms. are di-amyl, di-hexyl and di-octyl phthalates, trioctyl phosphate, and di-octyl sebacate. Particu- Examples of such esters 4 by emulsion polymerisation processes and isolated as powders by spray-drying.

One of the most important applications of the invention is in bonding a layer of textile fabric consisting of or containing cellulose acetate fibres to another layer of textile fabric. Thus two cellulose acetate fabrics may be bonded together by means of the plasticised polyvinyl chloride of the invention or a cellulose acetate textile fabric may be bonded to a textile fabric of an- Oth1 ;klnd to which the polyvinyl chloride ad heres. .Such other textile fabrics include fabrics of cotton fibres or regenerated cellulose fibres which, without having substantial aflinity for the polyvinyl chloride composition have an external structure capable of affording an anchorage for a coating of the polyvinyl chloride composition.

. The textile fabrics may be of various construclarly valuable for this purpose are long chain or moderately long chain di-esters of poly-glycols, especially the cli-hexoate, di-2-ethyl-hexoate and di-2-ethyl-butyrate of triethylene glycol.

tions; for example they may be of continuous filament yarns or of staple fibre yarns and they may be either wovenor knitted, e. g. of plain or fancy weave or 'of'plain or fancy warp or cir- The proportion of total plasticiser may be within Wide limits, for example from 60 to 175% based on the weight of the polyvinyl chloride. From to 25 or 35 of the total plasticiser may be of the plasticiser adapted to impart resilience though it is often unnecessary for this to exceed 2 or to obtain sufiicient resilience. The proportion of plasticiser imparting resilience is preferably kept to the minimum yielding the desired degree of resilience as this plasticiser may diminish the adhesion between the plasticised polyvinyl chloride and the cellulose acetate.

Polyvinyl chloride plasticised with a plasticiser of the kind referred to above as imparting adhesive properties for cellulose acetate, with or without the addition of plasticiser of the kind which imparts improvedresilience, may be applied to surfaces of cellulose acetate in various ways. Thus, for example, fabrics, films, ribbons or threads of the cellulose ester may be impregnated or coated with a dope comprising a solution of the plasticised polyvinyl chloride in a volatile solvent which is subsequently evaporated from the coated material; self-supporting films of the plasticised polyvinyl chloride may be bonded to fabrics, films or ribbons of the cellulose ester under pressure at a suitably elevated temperature; and ribbons and threads of the cellulose ester may'have a coating of plasticised polyvinyl chloride extruded upon them. When using a dope containing a volatile solvent, this must not, of course,

dissolve or unduly swell the cellulose acetate. It'

need not be when alone a solvent for polyvinyl chloride provided that it can form a solvent therefor in conjunction with the plasticiser. Suitable solvents can be obtained by diluting methyl ethyl ketone with a higher ketone such as methyl isobutyl ketone. Itis notessential however to have the polyvinyl chloride in true solution in the dope; it may be merely dispersed in the dope in such away that the dope is suitable for coating purposes. The polyvinyl chloride and plasticiser together may constitute from to of the dope. The dope may contain dyes, white or coloured pigments, or other effect materials and stabilisers for the polyvinyl chloride.

The polyvinyl chloride is advantageously of such high molecular weight as to be insoluble in acetone or in methyl-ethyl ketone. Such polyvinyl chlorides are of particular value by reasonof their mechanical properties and their resistance to the liquids commonly used for dry cleaning purposes. Theyare conveniently those made cular knit. Again various combinations of fabrics may be used to obtain duplex fabrics suit able for a wide variety of uses. Examples of useful combinations of fabricsare:

.1. Two layers of plain or fancy Woven fabric of cellulose acetate yarns. 2. Two layers of cellulose acetate warp knitted fabric. r

3. One layer of cellulose acetate woven fabric and one layer of cellulose acetate knitted fabric. 4. One layer of cellulose acetate woven or knitted fabric and one layer of a cotton fabric or a fabric. (preferably of light weight) of regenerated cellulose yarns made by stretching cellulose acetate yarns in steam or hot water and may be coloured as desired, for example uniformlyas by dyeing or locally as by printing or by using suitably coloured yarns in their construc-' tion. By using a knitted fabric in combination with a woven fabric it is possible to make composite materials having the appearance of a knitted fabric and with the dimensional stability associated with a woven fabric.

Suitable apparatus for bonding together two such fabrics comprises draw-off rolls for the two fabrics, a dope box or equivalent device for applying a coating of dope to one of the fabrics, a doctor blade for controlling the thickness of the coating, a radius bar where the uncoated fabric is brought intocontact with the coated surface of the other fabric, a guide-roll round which. the composite fabric so formed passes to the take-up roll, and heating means between the guide-roll and the take-up roll, for evaporating solvent from the coating of the dope and gelling the polyvinyl chloride.

The drawingshows in diagrammatic form an apparatus of this kind. In this apparatusone of the fabrics l is fed from a draw-off roll 2 via a guide roll 3 past a dope-applying device comprising a pair of parallel bars 4 and 5 over and in contact with which the fabric passes, and a,

doctor blad 6. The doctor blade 6 is arranged I todoctor the fabric at a point between the bars 4 and 5 and is adjustable towards and away from age-m sses thebarss Thedope applyingrarrangementis such? that' contact of the-doctoribladeswith anupstand'rmg portion 1 of 1 thefabric; e: gvia seams" merely 1 depresses the =fabric between a the bars '14 :an'dl: 5: and the fabric returnsato its 'normal lposition as soon as the projection has passedrn Dope-e1 "isrfed to fabncat the rear "sideof Y the doctorblad'ewil as'irequired; After leaving: the:- dope-applying means: the fabric I meets the second' fabric: 8 fed from a draw-offroll 9 via-=a guideirollenrloi The two fabries-with the dope layer between"them their pa's's*roundaradiusibar I l which ishcurvedi slightly-in the: direction of its :lengthkand serves to? press -th'e fabrics "together": while maintaining tlieinfull width andavoidih'g lngthwisewripples: From the-radiusbar the two fabrics passvia guide j The dope-was ap-piiedf-to the upper; surf ace of one of thefabrics; the other fabricwas brought intoContactwitntl'ie-coated'surface rduring vas sageround theradius bar; and under the tension applied by the take up -roll" the-"two fabrics were bonded together; the composite fabric so "formed" was carried past {the "heating element 'where the solvent was evaporatedandthe coating gelled, and was'then wound up:

Th'e "di (methyl-cyclo hexyD -phthalate maybethatderived' from anyone of the isomeric methyl; cyclo' hexanols' or from a mixture of isomeric 1 methyl cyc1o'-hexanols-e.-=g-. the mixture obtain- 1 ableby h'ydrogenatin'g coal tarcresolu From the composite fabric formed in this"=way,- attractive ribbons and "shapes for use in" the millinery trade were out," a hot cutter being used so as to seal the edges;

It is not essential to bond the fabrics together" continuouslywith'thecoatihg'of bne "of them, as described above; an'd-in--some* cases'it is more I convenient "to coat one of thefabrics, and to bond -this coated fabric to 'the other fabric in the course of a separate operation; for 'example bypassing the fabrics together between 'heated calender rolls: Another'alternative: is to form a self supporting film of the plasticised'polyvinyl chlorid'and to 'usethis' in bonding'together two celluldse acetate fabrics under heat and pressures Insteadbfa-"seif supportingfiliira fabric ofi "c'el'1'1ilose acetat-=or cellulose acetate "in" admixture with cotton or other non thermoplastic textile material maybe coated on bothsideswith the dope, for example by a padding process, and the coatedfabricwhicli -has received a heat treatment to" drive off 'the solvent and gel the "polyvinyl chloride may be usedas an interlining in "joining two -cellulose acetate fabrics- A further method isl to" extru'de t sheets-of the -=p1asticis'ed -qziolyvinyl chloride, in *the absence of "any volatile'solvent,

between two cellulose acetate'fabrics ona'calen 6i blywbetweenzthethattcalenderr rolls. toa-rbondithei fabrics :togetherr. Thertemperature necessarlwtm bondtaafil'mnor coating: of the plasticisedrpolyvinyl l chloride :in the: absence: of IIvolatilexsolvent to as. celluloseiiacetatelfabrics:need: be i no uh'igh'er -than: normal ironing temperature for cellulose .vacetatei fabrics "en'- g; toslBOE 0., ,sofithat -tl'fe bonding; can lbe idOIle-t without damage: to the surfac of 1' the?celluloseracetatei: l i

Anximportant application: ofs'the inventionflisa inxthezmanufacturetor:laminatedafabric articles: such as semi-stififrcollars, cons:andishirt' fronts: Theseemays comprise various: combinations q of twot or more rfabrics; for example: combination'st suchuasrthoseaoutlined above.- Accordingetto when methods of makings: snch rcollarsin accordance-*1 with the invention, two suitablyshapediblanks are cut from a sheet of .shirtingiabric,which, may be composed Lentir'ely flof cellulose acetate i fibres ormmayfcontaincellulose acetateai-lbresIin.v

admixture with cotton or other. non=tlfermop plastic textile fibre, for example regenerated" cellulose, coated on one side with" the plasticised polyvinyl chloride of the invention: The :coating may be carried out on a spreadingxmachine usingi the: dope: specified; above, the .1. machine having provisionforciheatingn thercoatedzifabricctozdrivetr Offx l volatile; solvent and gel c the: coatings: The; coatedbla'nks;arelsewirtogetherstoiformsthe collari uwithutheincoated surfaces .in contacts Bonding-i may) be}; effected byrordinaryt ironing; census: madewirr this zwayshave ;been\ found torpossesssaw very desirable combinatiomofwstiffness and rresile ien'ce-and towithstand washingweryxwell; They a m yi-be ironed imthe samewayuas tordinarymcelluew lose: acetate :fabrics; but withouttstarching. Ifil washednin =hotwater-some asofteningeof the 51301;? vinyl chloride tzinterlayera :occurs 1'; which: probably-L I facilitateswwashin afterironingrand allowingv to'l l} coo-ll theicollar will? be'foundrtozhave regainedutl'iei desiredgdegree :oflsti-ffnessrt "If desiredlboth lof thew blanks :may LbB'lOf warpv knittedafabric; or: one mayi be of warp knittedtfabric and theoth'eri'of wovenn fabrica Whenw av; somewhat.=stiffer and. heavier: collar is 1required?anrinterlining of .'cellulose;aee;- tate orr mixedai cellulose; acetate/cotton? fabric-1: coatedcon" both sides :cqwithr the icplasticisedizpolye vinyl chloride, maybe 3 usedf'tos bond :two outer: layers of cellulosez acetate:v fabric together; the"? method beingizsimilari to :that commonly iusedtrxinxr makings semi-stiff (collars: iwithxlan lzinterliningi ref :1

mixedicellulose'acetate/ cotton fabric; except thaw; by; the: process of' the :present "invention, nocsol'e vent for piotentialz'solventiis .required. Thisrisma s. mosttvaluable .simplificationzin the emanufacture e ofi'semi-rstifircollarsi Othersmethodsfsuch as are; described. above :for bonding two: fabrics together bythe method of the invention can be appliedxinf:

makinggsemi-stifi collars; forsexampleinstead or together two layers of a duplex fabric, the latter consisting of two layers of fabric, made of or 7 containing cellulose acetate fibres, and bonded by the plasticised polyvinyl chloride; the duplex fabric for this purpose may consist of one layer of cellulose acetate woven shirting fabric or warp knitted fabric and one layer of a light-weight woven fabric of cellulose acetate filaments or regenerated cellulose filaments, particularly regenerated filaments made by stretching cellulose acetate filaments and completely saponifying them as ,hereinbefore mentioned.

A warp knitted fabric of cellulose acetate may for example bebonded to a light-weight woven fabric of cellulose acetate or regenerated cellulose of the type mentioned above by means of the following composition:

Acetone-insoluble emulsion-polymerised spraydried polyvinyl chloride 100 parts Di-(methyl cyclo-hexanoD-phthalate 100 parts Mixture of methylethyl ketone with di-isobutyl I ketone 400 parts fled glycerol-phthalic anhydride condensation product or by Paraplex G25.

Other laminated fabric articles that can be made by the methods of the invention are neckties, belts, brassieres, hat-shapes, sweat-bands for hats, water-proof and shower-proof clothing, table covers,- shower-bath curtains, hand-bags and sponge-bags. It will be appreciated that a layer-of the plasticised polyvinyl chloride between two layers of cellulose acetate fabric gives ahigh degree of resistance to penetration by water. In making articles requiring some degree of elasticity, e. g. hat-shapes, brassires and sweat-bands it is of advantage to use fabrics having some degree of structural elasticity, e. g; knitted fabrics, woven fabrics cut on the bias and crepe fabrics. In this way it is possibl to take advantage of the elasticity of the polyvinyl chloride interlayer. Similarly where a somewhat elastic coated fabric is required whether for use as an interlining or for other purposes, it is. of advantage to use such a structurally elastic fabric.

and shaping between hot male and female moulding memberstwo blanks cut from cellulose acetate fabric coated on oneside with the plasticised polyvinyl chloride. ably one having structural elasticity to allow it to conform to the shape of the mould; and the temperature should be insufficient to fuse the cellulose acetate.

In bonding together coated fabrics according to the invention the simplest method of supplying the necessary heat is by direct contact of the material with a hotsurface, e. g. the surface of a calender roll, press platen, mould member or fiat-iron. Other methods of heating may be used however. Thus the heat may be generated within the polyvinyl chloride coatmethod, by virtue of the high loss factor of polyvinyl chloride compared with cellulose ace- Brassieres can be made according to the invention by bonding together- The fabric is prefer as the cellulose derivative.

tate,v the. polyvinyl chloride .can be. raised to a considerably higher temperature than the cellulose acetate. Di-electric heating can also be used in evaporating volatile solvent and gelling v the .plasticised polyvinyl chloride when this has been applied in the form of a dope. Infra-red heating can be used to evaporate volatilesolventand gel the coating and also to pre-heat coated fabrics immediately before they are bonded together under pressure.

As already indicated, one application of the invention is in bonding cellulose acetate materials to other materials to which the plasticised polyvinyl chloride adheres. Such other materials include materials such as cotton fibres, which without having substantial afiinity for the polymer have an'external structurecapable of affording an anchorage to a coating of the polymer, as well as materials having substantial aifinity for the polymer by virtue of their chemical constitution, e. g. polyvinyl chloride-acetate.

The invention'has been described with particular reference to the use of cellulose acetate rivatives having similar solubility properties to cellulose acetate can, however, be used in the same way. Among such esters are cellulose propionate, cellulose acetate-propionate, and c ellu-. 'lose acetate-butyrate. The cellulose derivative materials used may be made of fibres of high tenacity such as are obtainable by stretching cellulose derivative fibre to several or many times its original length for instance in steam or hot water. In this. way fibres of tenacity above 2.5 gm. per denier, e. g. 3 to 6 gm. per denier can be obtained. It has proved particularly difficult hitherto, to bond such materials to polyvinyl chloride.

Having described our invention, what we at:

being solely responsible for the high adhesion between the cellulose acetate-,andthe polyvinyl chloride. i

2.. A composite fabric comprising two layers of cellulose acetate material bonded together byan interlayer in-which the sole polymeric filmi'orrning material is an acetone-insoluble homopolymer of vinyl chloride, said polymer being plasticized with 55-l40%, based on the weight of said polyvinyl; chloride, ofa di-(monometh- .yl-cyclohexyl)-phtha1ate together with 5-35% based on the weight of the polymer of triethylene-glycol di-(Z -ethyl-butyrate), the cycloaliphatic ester being solely responsible for the high adhesion between the cellulose acetate and the polyvinyl chloride. I

3. A composite material comprising two layers" of cellulose acetate bonded together by another layer in' which the sole polymeric film forming; material is an acetone-insoluble homopolymer of vinyl chloride; said polymer being plasticized with 60 to based on the weight of said polyvinyl chloride, of a di-(cycloaliphatic)-ester of a dicarboxylic acid in which the two carboxyls are separated by no 'more than three carbon atoms, the cycloaliphatic ester being solely-re-v Other cellulose de-.

9 sponsible for the high adhesion between the cel- Number lulose acetate and the polyvinyl chloride. 2,263,015 HENRY EWING. 2,301,959 ALBERT MELLOR. 2,349,414 5 2,498,453 REFERENCES CITED 2,500,891 The following references are of record in the 2,517,646 file of this patent:

UNITED STATES PATENTS Number Number Name Date 369.945

Fordyce et a1 Mar. 30, 1937 Name Date Seel Nov. 18, 1941 Lanning Nov. 1'1, 1942 Ferrer May 23, 1944 Schaerer Feb. 21, 1950 Alexander Mar. 14, 1950 Ewing Aug. 8, 1950 FOREIGN PATENTS Country Date Great Britain Mar. 24, 1932 

1. A COMPOSITE MATERIAL COMPRISING TWO LAYERS OF CELLULOSE ACETATE MATERIAL BONDED TOGETHER BY AN INTERLAYER IN WHICH THE SOLE POLYMERIC FILMFORMING MATERIAL IS AN ACETONE-INSOLUBLE HOMOPOLYMER OF VINYL CHLORIDE, SAID POLYMER BEING PLASTICIZED WITH 60-175%, BASED ON THE WEIGHT OF SAID POLYVINYL CHLORIDE, OF A DI-(MONOMETHYLCYCLOHEXYL) -PHTHALATE, THE CYCLOALIPHATIC ESTER BEING SOLELY RESPONSIBLE FOR THE HIGH ADHESION BETWEEN THE CELLULOSE ACETATE AND THE POLYVINYL CHLORIDE. 